Earth's penultimate icehouse (ca. 340-285 Ma) was a time of low atmospheric pCO(2) and high pO(2), formation of the supercontinent Pangaea, dynamic glaciation in the Southern Hemisphere, and radiation of the oldest tropical rainforests. Although it has been long appreciated that these major tectonic, climatic, and biotic events left their signature on seawater Sr-87/Sr-86 through their influence on Sr fluxes to the ocean, the temporal resolution and precision of the late Paleozoic seawater Sr-87/Sr-86 record remain relatively low. Here we present a high-temporal-resolution and high-fidelity record of Carboniferous-early Permian seawater Sr-87/Sr-86 based on conodont bioapatite from an open-water carbonate slope succession in south China. The new data define a rate of long-term rise in Sr-87/Sr-86 (0.000035/m.y.) from ca. 334-318 Ma comparable to that of the middle to late Cenozoic. The onset of the rapid decline in Sr-87/Sr-86 (0.000043/m.y.), following a prolonged plateau (318-303 Ma), is constrained to ca. 303 Ma. A major decoupling of Sr-87/Sr-86 and pCO(2) during 303-297 Ma, coincident with the Paleozoic peak in pO(2), widespread low-latitude aridification, and demise of the pan-tropical wetland forests, suggests a major shift in the dominant influence on pCO(2) from continental weathering and organic carbon sequestration (as coals) on land to organic carbon burial in the ocean.